Method and apparatus for ultrasonic wet etching of silicon

ABSTRACT

Methods of forming substantially defect-free silicon structures at the submicron level by enhancing microscopic etchant concentration uniformity and reducing hydrogen bubble adhesion. Etchant mixtures are subjected to the application of ultrasonic waves. The ultrasonic waves promote cavitation that mixes the etchant mixture on a microscopic level, and also assists in promoting bubble detachment. Wetting agents are added to the etchant mixture to enhance the hydrophilicity of the silicon surfaces and thereby reduce bubble adhesion. Apparatus to carry out the method of forming silicon structures are also disclosed.

FIELD OF THE INVENTION

The present invention relates to the field of wet chemical etching and,in particular, to wet chemical etching of micromachined devices, such assilicon semiconductor structures. The process is particularly adaptedfor use in producing improved pattern definition in the etching ofintricate silicon microstructures.

BACKGROUND OF THE INVENTION

As the demand for ever-smaller silicon devices continues, and asresolution continues below the sub-micron level, the need for uniformand precise micromachining is increasing. Microdevices andmicrostructures used in semiconductor devices and scanning probemicroscopy demand smooth surfaces and precise etching at the sub-micronlevel. In addition, defect-free surfaces are required to bondmicromachined parts together during the formation of microdevices.

Micromachining is especially important in the fabrication of contactstructures for testing jigs. Because of a trend towards multi-chipmodules, semiconductor manufacturers are required to supply bare,unpackaged dice that have been tested and certified as Known Good Die(KGD). Known good die is a collective term that denotes bare, unpackageddie having the same reliability as the equivalent packaged die. The needfor known good die has led to the development of test apparatus in theform of temporary jigs or carriers suitable for testing discrete,unpackaged semiconductor dice. The test apparatus must make anon-permanent electrical connection between contact locations on thedie, such as bond pads, and external test circuitry associated with thetest apparatus. The bond pads provide a connection point for testing theintegrated circuitry formed on the die.

Typically the contact structures on the test apparatus take one of twoforms: (1) a recessed contact structure or "pit" such as the structuresdisclosed in U.S. Pat. No. 5,592,736 to Akram et al., which is assignedto Micron Technology, Inc.; or (2) a raised contact structure or"pillar" such as the structures disclosed in U.S. Pat. No. 5,686,317 toAkram et al., which is assigned to Micron Technology, Inc. The contactpit structure is especially useful for making contact with die such as,e.g., bumped die, flip-chips, chip scale packages or ball grid arrays,which have bumps or balls of solderable material such as a lead-tinalloy located on the bond pad of the semiconductor die. Both the pillarand pit structures require precise micromachining so that they make agood electrical connection with the semiconductor die being tested.

Uneven etching produces irregularly shaped contact pits, which requirethat the die be forced down onto the test apparatus so that the balls orbumps of the device make contact with the test apparatus. The forcerequired to make such contacts often is so great that it damages the dieand renders it inoperable. In addition, uneven surfaces on a device maycause layers deposited thereon to be rough or irregular, therebyimpairing electrical functioning and resulting in low processing yields.For example, a layer such as an insulating or conductive layer that isformed on a rough surface may have pinholes or breaks that result inelectrical shorts or that otherwise lead to improper electricalfunctioning of the device.

Micromachining processes using wet chemical etching have the advantagesof keeping production costs low, permitting high control of materialpurity, and being relatively reproducible. However, there are two majordisadvantages of wet etching processes: (1) non-uniform concentration ofetchant; and (2) hydrogen bubble adhesion.

Uniform wet chemical etching is difficult to achieve because the etchantsolution is often non-uniformly concentrated at the microscopic levelsof interest. Localized regions of low etchant concentration may occurdue to low mobility of the active elements of the solution, causing"dead spots." These dead spots may also be the result of the etchantsolution becoming saturated within localized regions. When this happens,the etching action is diminished in spots and results in non-uniformetching.

A known method of increasing local concentrations is to increase theoverall concentration of the etchant solution, but this does not resolvethe problem of non-uniform concentration. In addition, the resultantsolution may become so highly concentrated as to increase the etchingrate to an undesirable level in some areas, causing undercutting of thephotoresists and loss of control over line resolution and spacing. Othermethods to solve non-uniformity, such as the addition of magneticstir-bars to mix the solution, may improve macroscopic concentrationuniformity of the solution, but do not significantly affectnon-uniformity on the microscopic level.

A second problem causing non-uniform etching and poor pattern definitionis the adhesion of hydrogen bubbles to silicon surfaces during theetching process, which causes rough surfaces on the final product.Bubbles cling to the silicon surface due to the poor wettability of thehydrophobic silicon surface. Because the area of contact between abubble and the surface is shielded from the liquid etchant, it remainsunetched, or etches at a slower rate during the etching process. Theseinadequately etched areas may appear as pyramid-like islands of siliconon a planar surface or irregular pattern edges on the final product.

There is needed, therefore, a process for improving pattern definitionand etch uniformity in the etching of intricate silicon microstructuresby increasing etchant concentration uniformity and by decreasing theadhesion of hydrogen bubbles.

SUMMARY OF THE INVENTION

The present invention provides a method for improving etch uniformityand pattern definition when etching silicon microstructures bysubjecting a wet etching solution containing wetting agents toultrasonic waves. The wetting agents minimize bubble adhesion, while theultrasonic waves serve to mix the solution on a microscopic level, toenhance uniformity of concentration, and also to dislodge bubbles fromthe surface to be etched. Also provided is an apparatus for carrying outultrasonic-assisted wet etching.

Advantages and features of the present invention will be apparent fromthe following detailed description and drawings which illustratepreferred embodiments of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of the ultrasonic etching apparatus ofa preferred embodiment of the present invention.

FIG. 2 is a cross-sectional view of the ultrasonic etching apparatus ofa second embodiment of the present invention.

FIG. 3 is a cross-sectional view of the ultrasonic etching apparatus ofa third embodiment of the present invention.

FIG. 4 is a cross-sectional view of the ultrasonic etching apparatus ofa fourth embodiment of the present invention.

FIG. 5 is a cross-sectional view of the ultrasonic etching apparatus ofa fifth embodiment of the present invention.

FIG. 6 illustrates silicon microstructures formed by the process of thepresent invention.

FIG. 7 depicts a contact test pit formed by the process of the presentinvention.

FIG. 8 depicts a contact test pillar formed by the process of thepresent invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

In the following detailed description, reference is made to theaccompanying drawings which form a part hereof, and in which is shown byway of illustration specific embodiments in which the invention may bepracticed. These embodiments are described in sufficient detail toenable those skilled in the art to practice the invention, and it is tobe understood that other embodiments may be utilized and thatstructural, logical and electrical changes may be made without departingfrom the spirit and scope of the present invention.

The terms wafer or substrate used in the following description includeany semiconductor-based structure having an exposed silicon surfacewhich is to be etched in accordance with the process of this invention.The term microstructure as used in this application refers to anysilicon structure having a geometry around the sub-micron level, such asa silicon blade, tip, or elevated or depressed structure.

In addition, the invention is not limited to the etching ofsemiconductor structures, but may be used for any silicon microdeviceand may be readily adapted to non-etching applications such asultrasonic-assisted cleaning given the teachings herein. The followingdetailed description is, therefore, not to be taken in a limiting sense,and the scope of the present invention is defined by the appendedclaims.

Wet chemical etching is typically performed by immersion of wafers orother structures into a tank of etchant for a specific time. After thewafers have been etched to a desired degree, they are transferred to arinse station for etchant removal, and then typically rinsed againbefore being spin-dried. The method of the present invention includesthe immersion of wafers into an improved etchant solution with thesimultaneous application of ultrasonic waves.

Ultrasonic waves assist in mixing solutions to improve uniformity ofconcentration, and in the detachment of bubbles from the silicon surfaceby generating turbulent liquid flow. Microscopic cavities normally existin liquids, and the application of ultrasonic waves enhances thesecavities by providing energy. After a period of time the cavities growto a size where the incident wave motion force causes the cavity wallsto resonate, eventually causing instability and collapse of the cavitiesand generating transient, localized turbulent flow. This turbulent flowmixes the solution at a microscopic level to enhance concentrationuniformity, and also serves as a force to detach bubbles from thesilicon surface.

Bubble formation and growth is related to surface wettability.Wettability may be described by the equation shown below, where S is thewettability coefficient:

    S=W.sub.adhesion -W.sub.cohesion

Positive values of S represent a wettable surface because the work ofadhesion (solid-liquid attraction) is larger than the work of cohesion(liquid-liquid attraction). Wettable surfaces exhibit a very smallcontact angle between the liquid and the solid because the liquid tendsto spread out on the surface of the solid, and to dislodge gas bubbles.Negative values of S represent poorly wettable surfaces because the workof cohesion is larger than the work of adhesion.

Non-wettable or poorly wettable surfaces exhibit large contact anglesbetween the liquid and the solid, and this permits gas bubbles on thesolid surface to occupy a greater portion of the surface. Silicon isnormally poorly wettable because its hydrogen-terminated surface ishydrophobic. Using wetting agents in the etchant solution increases thehydrophilicity of silicon, improves wettability, and reduces the forcescausing bubbles to adhere to the silicon surface. Use of an alkalineetchant solution further facilitates these favorable changes.

The combination of ultrasonic waves with an etchant solution containinga wetting agent facilitates uniform etching because of increasedsolution concentration uniformity and decreased bubble adhesion. Theetchant may be either alkaline or acidic, but alkaline etchants arepreferred because they tend to make the silicon surface more wettable,due to replacement of the hydrophobic hydrogen surface termination withhydrophilic hydroxyl surface termination.

The etchant is preferably a strong base such as potassium hydroxide ortetramethyl ammonium hydroxide (TMAH), and is used in an aqueoussolution at a concentration of about 40 to 60 percent by weight. Apreferred potassium hydroxide etchant solution is used at a temperatureof about 40 to 80 degrees Celsius.

Although an alkaline etchant is preferred, acidic etchants incombination with wetting agents may also be used. Suitable acidicetchants include hydrofluoric acid (HF), nitric acid (HNO₃), acetic acid(CH₃ COOH) and phosphoric acid (H₃ PO₄). Hydrofluoric acid may be usedat room temperature in an aqueous solution at a concentration of about40 to 60 percent by weight, and may be buffered with ammonium fluoride(NH₄ F) to reduce unwanted ion generation. Phosphoric acid is typicallyused in an aqueous solution at an elevated temperature of 150 to 180degrees Celsius. Hydrofluoric and nitric acids are preferred for use inetching pure silicon or silicon dioxide, while phosphoric acid ispreferred for etching silicon nitride (Si₃ N₄).

Wetting agents suitable for use in the process of the invention includesurfactants and detergents that will provide the desired wetting effectwhile not interfering with the action of the etchant. Preferable wettingagents include surfactants such as alcohols, ethoxylates, alkoxylates,sulfates, sulfonates, sulfosuccinates or phosphate esters, and includecommercial surfactant mixtures such as the TRITON surfactantsmanufactured for industrial use by Union Carbide Company. Mostpreferably an alcohol such as isopropanol, 1-propanol, methanol orethanol is used. The concentration of wetting agent varies depending onthe agent, but for isopropanol can be approximately 15 percent by weightin an aqueous solution.

Ultrasonic waves produced by a transducer are sent through the etchantsolution during the etching process. As described above, the applicationof sonic energy mixes the etchant solution at a microscopic level andalso serves to dislodge bubbles that may be adhering to the siliconsurface. Preferred conditions include ultrasonic frequencies of 25 to 40kHz with sinusoidal or square digital waveforms.

Referring now to the drawings, where like elements are designated bylike reference numerals, an embodiment of the ultrasonic etchingapparatus 10 of the present invention is shown in FIG. 1. The apparatus10 is comprised of a wet etch tank 20 containing an etchant solution 22.A wafer boat 24 containing silicon wafers 26 or other structures to beetched is lowered into the etch tank 20 so that the silicon wafers 26are submerged in the etchant solution 22. The etch tank 20 and the waferboat 24 should be manufactured from materials that do not react ordegrade in the presence of common etchants that may be found in theetchant solution 22. These materials include, for example,polypropylene, low density polyethylene, and commercially availableplastics such as TEFLON, RYTON, and KYNAR.

An ultrasonic transducer 28 is positioned in such a manner that itimparts sonic energy to the etchant solution 22. The transducer may beactive, that is, it may have its own power source and be capable ofintroducing a power gain, or it may be passive and be connected to anoutside power source (not shown).

Referring to FIG. 1, an apparatus 10 comprises a transducer 28 affixedto the wafer boat 24 for the purpose of imparting sonic energy to theetchant solution 22. The wafer boat 24 may be constructed of anymaterial that is capable of withstanding the etchant solution and canalso transmit ultrasonic waves, but is preferably made of polypropylenein a thickness of about 0.1 to 0.5 inches.

As shown in FIG. 2, the transducer 28 may also be affixed to theinterior of the etch tank 20 by fastening means 30 such as the indicatedbrackets 30a, 30b. The transducer 28 may be located on the sides orbottom of the tank 20, as long as it does not interfere with themovement of the wafer boat 24 or with the functioning of otherstructures such as rinse nozzles (not shown).

FIG. 3 illustrates an apparatus 10 with the transducer 28 mounted to theoutside of the etch tank 20. An outer tank (not shown) may be used tocontain the entire apparatus 10 in order to prevent leakage if the etchtank 20 cracks or splits. Referring now to FIG. 4, a submersibletransducer 28 is shown. The transducer 28 is directly submerged into theetchant solution 22, and has a protective sleeve 32 of polypropylene orTEFLON to protect the transducer from the etchant solution 22.

As shown in FIG. 5, the transducer 28 may be mounted on a submersiblerod 34 that transmits ultrasonic energy from the transducer 28 to theetchant solution 22 without the need to bring the transducer 28 indirect contact with the etchant solution 22. The rod 34 may bemanufactured in a variety of shapes and sizes, including a cylinderhaving a circular, rectangular, or triangular cross-section, anelongated plate or sheet, or other suitable shape. A preferred materialfor the rod 34 is stainless steel, most preferably 316 grade stainlesssteel, due to its efficient transmittal of ultrasonic energy. To protectthe rod 34 from the etchant solution 22, a protective sleeve 32 ofpolypropylene, TEFLON or other suitable etchant-resistant material maybe used.

FIG. 6 illustrates silicon microstructures 40 that may be created viathe process of the present invention. The microstructures 40 may beproduced with submicron geometries due to the enhanced precision andsubstantially defect-free results afforded by the ultrasonic wet etchprocess of the present invention. The smoother silicon surfaces createdby the ultrasonic etching processes of the present invention result inimproved deposition of layers thereon, thereby reducing defects andimproving processing yields.

FIG. 6(a) depicts a silicon substrate 42 that has been etched to producesilicon blades 44 overhanging a pit or depression 46 in the surface ofthe substrate 42. FIG. 6(b) illustrates a wafer or substrate 42 that hasbeen etched to provide a hole 60 passing through the wafer. FIG. 6(c)shows a silicon bridge 44 under which has been etched out a depression46 in the substrate 42. In FIG. 6(d) are shown an elevated siliconstructure 48 and a depression 50 in the substrate 42 that may be createdvia the present inventive process. FIG. 6(e) illustrates a top view ofthe structures shown in FIG. 6(d).

A particularly preferred microstructure 40 that may be produced throughthe use of the inventive process is a test apparatus 40 containing acontact test pit 46, as depicted in FIG. 7. FIG. 7(a) shows a top viewof the pit 46 showing the location of silicon blades 44 that extenddownward into the main pit cavity 46. FIG. 7(b) illustrates a side viewof the pit 46 showing how the blades 44 and the walls of the pit cavity46 are coated with an insulation layer 43 and a conductive layer 52which is connected with a terminal (not shown) for testing purposes.

An integrated circuit device 54 to be tested, which may be any devicehaving bumps or balls such as, e.g., a flip-chip, chip scale package,bumped chip or ball grid array, is lowered onto the test apparatus 40,and solder balls 56 attached to the bottom of the circuit 54 slip intothe test pits 46 as shown in FIG. 7(b). The solder ball 56 contacts eachof the silicon blades 58a, 58b. The multiple contacts 58a, 58b affordedby the test pit structure 46 permit the circuit 54 to be easily testedby providing a greater surface area of contact without requiring thatthe circuit 54 be pressed down onto the test apparatus 40 with excessiveforce.

A second preferred microstructure 40 that may be produced through theuse of the inventive process is a test apparatus 40 containing a contacttest pillar 48, as depicted in FIG. 8. FIG. 8(a) shows a top view of thepillar 48 showing the location of silicon projections 44 that areadapted to penetrate the bond pads on the die so as to form an ohmicconnection. FIG. 8(b) illustrates a side view of the pillar 48 showinghow the projections 44 and the sides of the pillar 48 are coated with aconductive layer 52 that is connected with a terminal (not shown) fortesting purposes.

An integrated circuit device 54 to be tested is lowered onto the testapparatus 40, and the pillars 48 make contact with the bond pads 56 onthe die. The precise micromachining afforded by the present inventiveprocess permits the silicon pillar 48 to be precisely shaped so that amaximal contact area may be made between the pillar 48 and a bond pad 56with a minimum of damage to the bond pad 56. In addition, micromachinedprojections 44 on the pillar 48 are adapted to pierce the native oxidecoating 62 typically present on an aluminum or copper bond pad 56 tomake contacts 58 with the underlying conductive layer 64. The multiplecontacts 58 between the projections 44 and the conductive layer 62, inaddition to the precise alignment of the pillars 48 and the bond pads56, obviate the need to use excessive force to press the device 54 downonto the test apparatus 40.

As can be seen by the embodiments described herein, the presentinvention encompasses processes of improving pattern definition in thewet chemical etching of micromachined devices. An etchant solutioncontaining wetting agents is subjected to ultrasonic waves during theprocess of etching silicon structures, which results in etchantuniformity and reduced hydrogen bubble adhesion. Silicon structuresetched by the process are substantially defect-free and exhibit preciseand accurate line and pattern definition, and have improved uniformityacross a wafer or die.

The above description and drawings illustrate preferred embodimentswhich achieve the objects, features and advantages of the presentinvention. It is not intended that the present invention be limited tothe illustrated embodiments. Any modification of the present inventionwhich comes within the spirit and scope of the following claims shouldbe considered part of the present invention.

What is claimed as new and desired to be protected by Letters Patent ofthe United States is:
 1. A method of etching to form a silicon structurecomprising:providing a silicon substrate; etching said substrate in anetchant mixture, wherein said mixture includes an etchant and a wettingagent; and simultaneously applying ultrasonic waves to the etchantmixture during at least a portion of said etching.
 2. The method ofclaim 1, wherein the etchant is an alkali.
 3. The method of claim 1,wherein the etchant is tetramethylammonium hydroxide.
 4. The method ofclaim 1, wherein the wetting agent is an alcohol.
 5. The method of claim1, wherein the wetting agent is isopropanol.
 6. The method of claim 1,wherein said ultrasonic waves are applied at a frequency in the range ofabout 20 to 40 kiloHertz.
 7. A method of forming a silicon structurehaving a substantially defect-free surface comprising:providing asilicon substrate; etching said substrate in an etchant mixture, whereinsaid solution includes an alkaline etchant and a wetting agent; andapplying ultrasonic waves with a frequency of about 20 to 40 kiloHertzto the etchant mixture.
 8. The method of claim 7, wherein said alkalineetchant is potassium hydroxide.
 9. The method of claim 7, wherein saidalkaline etchant is tetramethylammonium hydroxide.
 10. A method offorming a silicon contact test structure comprising:providing a siliconsubstrate; etching said substrate in an etchant mixture, wherein saidmixture includes an etchant and a wetting agent; applying ultrasonicwaves to the etchant mixture; and forming a silicon contact teststructure on said substrate; and forming a silicon contact teststructure on said substrate.
 11. The method of claim 10, wherein thesilicon contact test structure is formed with a substantiallydefect-free surface.
 12. The method of claim 10, wherein the etchant isan alkali.
 13. The method of claim 10, wherein the etchant istetramethylammonium hydroxide.
 14. The method of claim 10, wherein thewetting agent is an alcohol.
 15. The method of claim 10, wherein thewetting agent is isopropanol.
 16. The method of claim 10, wherein saidultrasonic waves are applied at a frequency in the range of about 20 to40 kiloHertz.
 17. The method of claim 10, wherein the silicon contacttest structure is a contact pit.
 18. The method of claim 10, wherein thesilicon contact test structure is a contact pillar.
 19. A method offorming silicon structures by wet etching comprising:providing a siliconwafer; providing an etching apparatus, wherein said apparatus comprisesa polypropylene tank for holding an etchant mixture, a holder forcontaining the silicon wafer, and at least one ultrasonic transducercapable of producing frequencies in the range of about 20 to 40kiloHertz in the mixture; holding the silicon wafer in the holder andimmersing the silicon wafer in the etchant mixture, wherein said etchantmixture comprises an alkaline etchant and a wetting agent; and applyingultrasonic waves to the etchant mixture.
 20. A method of etching to forma silicon contact test structure, comprising the steps of:providing asilicon substrate; forming a silicon contact test structure on saidsubstrate by exposing said substrate to an etchant mixture, wherein saidmixture includes an alkaline etchant and a wetting agent; andsimultaneously applying ultrasonic waves at a frequency of about 20 to40 kiloHertz to the etchant mixture during at least a portion of saidetching.
 21. The method of claim 20, wherein the alkaline etchant ispotassium hydroxide.
 22. The method of claim 20, wherein the alkalineetchant is tetramethylammonium hydroxide.
 23. The method of claim 20,wherein the silicon contact test structure is a contact pit.
 24. Themethod of claim 20, wherein the silicon contact test structure is acontact pillar.
 25. The method of claim 1, wherein said substrate isetched to produce silicon blades overhanging a pit or depression in thesurface of said substrate.
 26. The method of claim 1, wherein saidsubstrate is etched to provide a hole passing therethrough.
 27. Themethod of claim 1, wherein said substrate is etched to provide a siliconbridge in said substrate.